In the past 20 years, green analytical procedures have attracted much attention from all walks of life, including analytical chemistry. The conversion to green analytical chemistry (GAC) requires the establishment of novel, more effective procedures compared to conventional methods. Improving sample preparation, design procedures, solvent quantities, and accurate assessment are the best ways to follow the principles of GAC. The current review focuses on the influential factors in greenness, like the design, applications, instrumentals, green features, and greenness measurement of the solidified floating organic drop microextraction (SFODME) method for toxic metals. Using various solvents, such as ionic liquids, deep eutectic solvents, and biomolecules, we formed more environmentally solidified floating organic drop microextraction modes. The green analytical procedure index (GAPI) and analytical greenness (AGREE) are two green assessment tools used to evaluate and compare the greenness of a solidified floating organic drop microextraction for various modes. The two scales (GAPI and AGREE) are very simple and accurate. They focus on several factors, such as the collection of samples, chemical amounts, time analysis, energy, occupational danger, waste, and others. Future developments were also investigated.